Urethane foams prepared from alkylene oxide adducts of arylamines



United States Patent 3,336,245 URETHANE FOAMS PREPARED FROM ALKYLENEOXIDE ADDUCTS 0F ARYLAMINES J W. Britain, New Martinsville, W. Va.,assignor to Mobay Chemical Company, Pittsburgh, Pa., a corporation ofDelaware No Drawing. Filed May 3, 1965, Ser. No. 452,898 6 Claims. (Cl.260-25) This invention relates to the preparation of new syntheticresins and more particularly, to a method of making a novel resinousproduct for use in making a polyurethane foam having improveddimensional stability, and is a continuation-in-part of applicationSerial No. 54,546, now abandoned.

It has been proposed heretofore to prepare polyurethane foams byreacting an organic polyisocyanate with an organic compound having atleast two reactive hydrogen atoms such as, for example, a polyester, apolyalkylene. ether glycol, or the like. It also has been proposed touse compounds having at least three hydroxyl groups such as, forexample, the condensation product of propylene oxide and a t-rihydricalcohol such as trimethylolpropane. For example, Price in U.S. Patent2,866,774 discloses that a foam can be prepared from a reaction productof an organic polyisocyanate and a polyalkylene ether having three ormore hydroxyl groups by adding water to the reaction product. Such aprocess is disadvantageous because the components are mixed together intwo steps and because the product is not entirely suitable for fillingcavities due to lack of dimensional stability and cost of manufacture.

It has also been proposed to prepare polyurethane foams by reacting anorganic 'diisocyanate with a polypropylene ether glycol undersubstantially anhydrous 'conditions to form a prepolymer and thenreacting the resulting prepolymer with water andN,N,N,N-tetrakis(2-hydroxy propy-l) ethylene diamine. This process isdisclosed in US. Patent 2,915,496 and is a costly two-step process.

The products of such reactions have many uses, but it has been foundthat rigid foams prepared from such products or from other alkyleneoxide-aliphatic amine condensates are not entirely suitable for fillingcavities because they have poor dimensional stability. Methods forfilling cavities with polyester foams blown with carbon dioxide havebeen disclosed such as, for example, in US. Patent 2,690,987 but thefoam thus produced is not dimensionally stable, and such foam is toocostly to successfully compete with other plastic foams.

It is therefore an object of this invention to provide a method formaking improved polyurethane foams devoid of the foregoingdisadvantages.

Another object of the inventionis to provide a method for making rigidfoams less subject to shrinkage and therefore more suitable for fillingcavities. '7

A further object of the invention is to provide a novel resin, a methodfor making it and a method for making a rigid polyurethanefoam'therefrom having improved dimensional stability which can be usedto advantage for insulation and for preparing molded objects.

A more specific object'of the invention is to provide a method forfilling cavities with .a polyurethane foam which has improveddimensional stability and which retains its shape to a greater degreeunder humid conditions.

The foregoing objects and others are accomplished in accordance withthis invention, generally speaking, by providing a method for making asolidified polyurethane foam which involves reacting an organicpolyisocyanate with a unique substituted aromatic polyamine containing asingle molecule of an alkylene oxide for each hydrogen wherein R iseither hydrogen or an alkyl radical having from 1 to about 3 carbonatoms; n is an integer of from 2 to 3 and R is a radical having avalence equal to n and obtained by removing n hydrogen atoms from thefollowing groups:

and mixtures thereof, in which R" is halogen, an alkyl radical havingfrom 1 to 4 carbon atoms or an alkoxy radical havingfrom 1 to 4 carbonatom-s; G is an alkylene radical having from 1 to 3 carbon atoms; In isan integer of from '0 to 4 and t is 2.

It is essential for most rapid uniform mixing of the reactants that theresinous material reacted with the polyisocyanate have a viscosity ofnot substantially more than about 75,000 centipoises at 25 C.; for thatreason, the addition product of the polyamine must either have such aviscosity or its viscosity must be reduced to this point by mixing itwith another resinous organic compound having at least two reactivehydrogens and a lower viscosity to insure best mixing characteristics.

The condensate of the aromatic polyamine and the alkylene oxide may beproduced by any known method. The manipulative steps disclosed in US.Patent 2,174,762, for example, may be used; another suitable process isthat disclosed in US. Patent 2,257,817. The method used to prepare thearomatic diamine-propylene oxide condensates of Example 12 herein ispreferred, however, and a method for making a foam wherein the aromaticdiaminepropylene oxide condensate is prepared and then reacted Withoutextensive purification steps to form a foam is also preferred. Theresulting foam product has good dimensional stability and can be madewith less cost since purification to remove isomers other than 2,4- and2,6- i-somers is avoided.

The conditions under which the propylene oxide and the tolylene diamineor other aromatic diamine are reacted may be varied from those set forthin the example referred to, however, For example, the temperature canvary from about C. up to about 250 C. or even higher. The pressure canalso be varied but it has been found that best results are obtained whenthe pressure is within the range of from about 1 to about 3 atmospheresgauge pressure at a temperature of from C. to about C. Although it isnot necessary to use a catalyst in the preparation of the aromaticpolyamine-propylene oxide condensates, the reaction proceeds at a morerapid rate if one is used. Any suitable basic catalyst can be used butit is preferred to use an alkali metal catalyst such as, for example,metallic sodium or potassium. Any catalytic amount of the catalyst canbe used but it is preferred to use from about 0.01 percent to about 1percent by weight thereof, in which case an acid chloride such asbenzoyl chloride should be added after reaction has completed toneutralize all of the catalyst in order to obtain best results. Theprocess of Example 12 can, of course, be used to prepare these and otheralkylene oxide condensates of these and other aromatic polyamines.

Any suitable polyamine may be used to prepare the addition product ofthis invention. Generally, the preferred polyamines fall within thescope of the following formula: R(NH wherein n is an integer of from 2to 3 and R is or mixtures thereof wherein R" is a halogen, an alkylradical having from 1 to 4 carbon atoms or an alkoxy radical having from1 to 4 carbon atoms; G is an alkylene radical having from 1 to 3 carbonatoms; In is an integer of from to 4 and t is 2. Specific examples ofsome such suitable aromatic polyamines include 2,4-t0lylene diamine,

2,6-tolylene diamine, or mixtures thereof; 1,5-naphthalene diamine,

1,4-naphthalene diamine,

4,4'-diphenyl methane diamine, 4,4-diamino-3,3'-dichlorodiphenylmethane, 4,4'-diamino-3,3'-dimethyl diphenyl methane,4,4-diamino-3,3'-dimethoxy diphenyl methane, 4,4-diamino diphenyldimethyl methane, 4,4,2-triamino-3,3'-dimethyl diphenyl methane, diaminobiphenyl,

phenylene diamine,

tolylene triamine,

naphthalene triamine,

xylylene diamine,

xylylene triamine, 3,3'-dichloro-4,4'-diaminodiphenylene,3,3'-dibromo-4,4'-diaminodiphenylene,3,3'-dimethyl-4,4'-diaminodiphenylene,3,3-diisopropoxy-4,4'-diaminodiphenylene,3,3'-diethyl-4,4-diaminodiphenylene,3,3-dipropyl-4,4'-diaminodiphenylene,3,3-dibutyl-4,4-diaminodiphenylene,3,3-diisopropyl-4,4-diaminodiphenylene,3,3-diisobutyl-4,4-diaminodiphenylene,3,3-dimethoxy-4,4'-diaminodiphenylene,3,3-diisopropoxy-4,4'-diaminodiphenylmethane,3,3'-dirnethyl-4,4'-diaminodiphenylmethane,3,3'-diethyl-4,4'-diaminodiphenylmethane,3,3-dipropy1-4,4-diaminodiphenylmethane,3,3-dibutyl-4,4'-diaminodiphenylmethane,3,3'-diisopropyl-4,4-diaminodiphenylmethane,3,3-diisobutyl-4,4-diaminodiphenylmethane,3,3'-dimeth0xy-4,4'-diaminodiphenylmethane,3,3'-diisopropoxy-4,4'-diaminodiphenylethane,3,3-dimethyl-4,4-diaminodiphenylethane,3,3'-diethyl-4,4'-diaminodiphenylethane,3,3'-dipropyl-4,4-diaminodiphenylethane,3,3'-dibutyl-4,4-diaminodiphenylethane,3,3'-diisopropyl-4,4-diaminodiphenylethane,3,3-diisobutyl-4,4'-diaminodiphenylethane,3,3'-dimethoxy-4,4'-diaminodiphenylethane,3,3-diisopropoxy-4,4'-diaminodiphenylpropane,3,3-dimethyl-4,4'-diaminodiphenylpropane,3,3'-diethyl-4,4-diaminodiphenylpropane,3,3'-dipropyl-4,4'-diaminodiphenylpropane,3,3'-dibutyl-4,4-diaminodiphenylpropane,3,3'-diisopropyl-4,4'-diaminodiphenylpropane,3,3'-diisobutyl-4,4'-diaminodiphenylpropane,

3 ,3 -dimethoxy-4,4'-diarnino diphenylpropane,

3-methyl-3 -ethyl-4,4-diaminodiphenylene,

3-rnetl1yl-3 -ethyl-4,2'-diaminodiphenylene,

3-methyl-3 '-ethyl-4,3 '-diaminodiphenylene,

3-methyl-3 '-ethy1-2,4-diaminodiphenylene,

3-methyl-3 -ethyl-3,3'-diaminodiphenylene,

3-methyl-2-ethyl-4,4'-diaminodiphenylene,

2-chloro-3 '-methoxy-4,4-diaminodiphenylene,

3-propoxy-3 '-bromine-4,4-diaminodiphenylene,

3-methyl-3 -ethyl-4,4'-diaminodiphenylmethane,

3-methyl-2'-ethyl-4,4-diaminodiphenylmethane,

2-chloro-3 -methoxy-4,4-diaminodiphenylmethane,

3 -propoxy-3 '-bromine-4,4-diaminodiphenylmethane,

3-methyl-3 -ethyl-4,4-diaminodiphenylethane,

3-methyl-2-ethyl-4,4'-diaminodiphenylethane,

2-chloro-3 '-methoxy-4,4'-diaminodiphenylethane,

3 -propoxy-3 '-bromine-4,4'-diaminodiphenylethane,

3-methyl-3 '-ethyl-4,4'-diaminodiphenylpropane,

3-methyl-2'-ethy1-4,4'-diaminodiphenylpropane,

2-chloro-3 '-methoxy-4,4-diamino diphenylpropane,

3 -propoxy-3 '-bromine-4,4'-diaminodiphenylpropane,

3-methyl-5 -ethyl-4,4-diaminodiphenylene,

3-methy1-5-ethyl-4,4'-diaminodiphenylmethane,

3-methyl-5-ethyl-4,4-diaminodiphenylethane,

3 -methyl-5-ethyl-4,4-diaminodiphenylpropane,

3,5, 3 '-tripropyl-4,4-diaminodiphenylene,

3,5,3 '-triethoxy-4,4-diaminodiphenylene,

3 ,5 ,3 -trimethoxy-4,4-diaminodiphenylene,

3,5, 3 '-trichloro-4,4'-diaminodiphenylene,

3,5,3 -tribromo-4,4-diaminodiphenylene,

3,5 3 -tripropoxy-4,4-diaminodiphenylene,

3 ,5 ,3 -tripropyl-4,4'-diaminodiphenylmethane,

3,5,3 '-trimeth0xy-4,4'-diaminodiphenylmeth ane,

3,5 ,3'-trichlor0-4,4'-diaminodiphenylmethane,

3,5,3 -tripropyl-4,4'-diaminodiphenylethane,

3 ,5 ,3 -trimethoxy-4,4'-diarninodiphenylethane,

3,5 ,3'-trichloro-4,4-diaminodiphenylethane,

3,5,3'-tripropyl-4,4'-diaminodiphenylpropane,

3,5,3'-trimethoxy-4,4-diaminodiphenylpropane,

3 ,5 ,3'-trichloro-4,4-diaminodiphenylpropane,

2-bromo-3-propoxy-3-methyl-4,5 -diaminodiphenylene,

2-chloro-3-ethoxy-3 '-propyl-4,5 '-diaminodiphenylene,

2-chloro-3-methoxy-3 '-ethyl-4,5 '-diaminodiphenylene,

2-bromo-3-butoxy-3 -butyl-4,5'-diaminodiphenylene,

2-chloro-3-methoxy-3 '-ethyl-4,5 -diaminodiphenylmethane,

2-chloro-3-methoxy-3'-ethyl-4,5'-diaminodiphenylethane,

2-chloro-3-methoxy-3 -ethyl-4,5 -diaminodipl1enylpropane,

2, 3-diaminotoluene,

2,5 -diaminotoluene,

3,4-diaminotoluene,

1-chloro-2,4-diaminobenzene,

1-ethoxy-2,4-diaminobenzene,

1-propyl-2,4-diaminobenzene,

1-ethyl-2,4-diaminobenzene,

1-bromo-2,4-diaminobenzene,

l-butoxy-2,4-diaminobenzene,

3-chloro-2,4-diaminobenzene,

dimethoxynaphthalene diamine,

dichloronaphthalene diamine,

benzidine,

and the like compounds and mixtures thereof.

A polyaryl alkylene polyamine including crude 4,4- diphenylmethanediamine having the formula in which T is an orgaic radical andpreferably an aliphatic radical obtained by removing the carbonyl oxygenfrom an aldehyde or ketone and is preferably CH M is l or 2, X ishalogen, lower alkyl or hydrogen and N is 1, 2, or 3. The aliphaticradical, T, in the foregoing formula, may be obtained by removing thecarbonyl oxygen from any suitable aldehyde or ketone such as,formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,N-heptaldehyde, benzaldehyde, cyclohexane aldehyde, acetone, methylethyl ketone, methyl-n-propyl ketone, diethyl ketone, hexanone-2,hexanone-3, di-npropyl ketone, di-n-heptyl ketone, benzophenone,dibenzyl ketone, cyclohexanone and the like. To illustrate, if oneremoves the carbonyl oxygen from formaldehyde, H @O, the radicalremaining is a methylene radical or from acetone, CH COCH the radicalremaining is When X is halogen, it may be any suitable halogen but ispreferably chlorine or bromine and further, it is preferred that theamount of chlorine or bromine fall between about one percent and fifteenpercent by weight of the compound. When X is lower alkyl, it is mostpreferably methyl or ethyl but other lower alkyl radicals such aspropyl, butyl and the like may be the radical, X. The polyaryl alkylenepolyamines are preferably mixtures of di and higher polyamines. Thus, N,in the formula preferably has a value of from about 0.1 to about 1.5. Toillustrate, in a mixture of amines of the above formula containing 90%diamine and percent triamine, N would have a value of 0.1. For a mixturecontaining 20 percent di-, 30 percent tri-, 30 percent tetraand 2-0percent pentaamine, the average value of N would be 1.5. A mostpreferred value for N is between about 0.85 and about 1.1 with about 40percent to about 60 percent of the mixture of polyamines being adiamine.

Amines of the above formula are well-known and available commercially.They may be prepared as disclosed in US. Patent 2,683,730. A specificamine suitable for use in accordance with the present invention may beobtained by reacting about 60 parts of aniline with about 25 parts offormaldehyde (aqueous, 37 percent CH O) and about 74 parts of HCl,aqueous, 30 percent HCl) at a temperature of about 90 C. to about 100 C.for about 1.5 to about 2 hours and then reacting this product with NaOHand separating out the crude amine.

One particularly preferred aromatic diamine is the isomeric mixture of80 percent 2,4-tolylene diamine and about 20 percent 2,6-tolylenediamine. Another preferred aromatic diamine is 4,4-diphenylmethanediamine. The polyamine may be a chemically pure product or it can be aso-called crude diamine which contains various isomers in admixture withone another.

As indicated above, any of the suitable polyamines may containsubstituents on the aromatic nucleus in addition to the amino groups;however, space prohibits a mention of the multitude of operativepolyamines and substituted polyamines which may be used. All aromaticpolyamines falling within the above-defined categories are contemplated.

Any suitable alkylene oxide, preferably one having 2 to 5 carbon atoms,such as, for example, ethylene oxide,

propylene oxide, butylene oxide and amylene oxide may be condensed withthe aromatic polyamine to form the addition product. Likewise, thepolyamine can be condensed with an alkylene halohydrin such as, forexample, ethylene chlorohydrin, propylene chlorohydrin, epichlorohydrin,and the like.

The condensate produced from the polyamine should have at least threeand preferably at least four hydroxyl groups. In other words, all of thehydrogen atoms on the nitrogen atoms of a diamine should preferably bereplaced with a hydroxyl terminated alkylene radical. The invention thuscontemplates any additional product of an aromatic polyamine havinghydroxyl groups and preferably one having at least four hydroxyl groupsand a molecular weight of at least about 284 which is the 6 theoreticalmolecular Weight of the condensation product of 1 mol of phenylenediamine and 4 mols of ethylene oxide. The hydroxyl number ofthe additionproduct of the polyamine and alkylene oxide can vary from about 300 toabout 700 but is preferably within the range of from about 350 to about450.

Although a foam can be prepared to advantage from alkyleneoxide-aromatic polyamine condensates of any molecular weight the mostconsistently good results have been obtained up to this time with anadduct of 4 mols propylene oxide and 1 mol tolylene diamine, either the2, 4 or the 2, 6-isomer, or an :20 mixture of the two respectively; anadduct of 1 mol 4,4'-diphenylmethane diamine and 4 mols propylene oxide;an adduct of 1 mol m-phenylene diamine or p-phenylene diamine, ormixtures thereof with 4 mols propylene oxide and these condensates aretherefore preferred. Most preferred is a ratio of 1 mol 2,4-toylenediamine or 1 mol 2,6-tolylene diamine or mixtures thereof and 4 molspropylene oxide to produce a condensate which can be represented by theformulae:

N(CH2CH(CHa) OH):

I N(CH2CH(CH )OH)1 and or mixtures thereof respectively.

The product of 1 mol of m-phenylene diamine or 1 mol p-phenylene diamineand 4 mols propylene oxide can be represented by the formulae:

N(CH2CH(C 3) N(CH2CH(GH )OH)2 1TT(CH2CH(CH3) OHM I I(CHzCH(CH3) OH):respectively.

When the viscosity of the polyamine/alkylene oxide condensate exceedsoperable limits, its viscosity must be adjusted with a suitable diluent.This is accomplished by mixing the polyamine/alkylene oxide condensatewith another restinous organic compound having at least two reactivehydrogen atoms and a lower viscosity. In fact, one of the preferredembodiments of the invention contemplates a mixture of thepolyamine/alkylene oxide addition product of this invention and anotherresin, such as, for example, a polyester, a polyhydric poly (alkyleneether), a poly-hydric poly (alkylene thioether) or other suitableorganic compounds having at least two and preferably not more than sixreactive hydrogen atoms and a molecular weight of from about to about1500, an hydroxyl number of from about 75 to about 1700 and a viscosityat 25 C. of from about 100 centipoises to about 5000 centipoises. Thepolyalkylene ether or similar compound having at least two reactivehydrogen atoms used in admixture with the addition product of anaromatic polyamine and an alkylene oxide must be miscible 7 with theaddition product in all proportions in which it is to be used.

The amount of organic compound having at least two reactive hydrogenatoms used as a diluent to reduce the viscosity of the resinouscomponent will vary with the viscosity of the aromaticpolyamine-alkylene oxide addition product and the viscosity of thediluent. For best results however, the mixture should contain from about90 parts by weight to about 50 parts by weight of the addition productof the polyamine and about 10 parts by weight to about 50 parts byweight of the other organic compound having at least two reactivehydrogen atoms. Preferably, the ratio of polyamine-alkylene oxideaddition product or adduct to the other organic compound having at leasttwo reactive hydrogen atoms will be from about 65 to about 70 parts ofthe former to about 35 to about 30 parts of the latter (diluent).

Any suitable organic compound having at least two reactive hydrogenatoms determinable by the Zerewitinoff method may be used as thediluent. Examples of suitable types of organic compounds containing atleast two active hydrogen containing groups which are reactive with anisocyanate group are hydroxyl polyesters, polyhydric polyalkyleneethers, polyhydric polythioethers, polyacetals, aliphatic polyols,including alkane, alkene and alkyne diols, triols, tetrols and the like,aliphatic thiols including alkane, alkene and alkyne thiols having twoor more SH groups; polyamines including aromatic, aliphatic andheterocyclic diamines, triamines, tetramines and the like; as well asmixtures thereof. Compounds which contain two or more different groupswithin the above-defined classes may also be used in accordance with theprocess of the present invention such as, for example, amino alcoholswhich contain an amino group and a hydroxyl group, amino alcohols whichcontain two amino groups and one hydroxyl group and the like. Also,compounds may be used which contain one fi'SH group and one OH group ortwo OH groups and one SH group as well as those which contain an aminogroup and an SH group and the like.

Any suitable hydroxyl polyester including lactone polyesters may beused, for example, those obtained from polycarboxylic acids andpolyhydric alcohols. Any suitable polycarboxylic acid may be used suchas, for example, oxalic acid, malonic acid, succinic acid, glutaricacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacicacid, brassylic acid, thapsic acid, maleic acid, fumaric acid,glutaconic acid, a-lpha-hydrornuconic acid, beta-hydromuconic acid,alpha-butyl-alpha-ethyl-glutaric acid; alpha, beta-diethylsuccinic acid,isophthalic acid terephthalic acid, hemimellitic acid, trimellitic acid,trimesic acid, mellophanic acid, prehnitic acid, pyromellitic acid,benzenepentacarboxylic acid, 1,4-cyclohexanedicarboxylic acid;3,4,9,lperylenetetracarboxylic acid and the like. Any suitablepolyhydric alcohol may be used such as, for example, ethylene glycol,1,3-propylene glycol, 1,2-butylene glycol, 1,2-propylene glycol,1,4-butylene glycol, 1,3- butylene glycol, 1,5-pentane diol, 1,4-pentanediol, 1,3- pentane diol, 1,6-hexane diol, 1,7-heptane diol, glycerine,trimethylolpropane, 1,3,6-hexanetriol, triethanolamine, pentaerythritol,sorbitol and the like.

The hydroxyl polyester may also be a polyester amide such as isobtained, for example, by including some amine or amino alcohol in thereactants for the preparation of the polyesters. Thus, polyester amidesmay be obtained by condensing an amino alcohol such as ethanolamine withthe polycarboxylic acids set forth herein or they may be made using thesame components that make up the hydroxyl polyester with only a portionof the components being a diamine such as ethylene diamine and the like.

Any suitable polyhydric polyalkylene ether may be used such as, forexample, the condensation product of an alkylene oxide beginning withany suitable initiator. The initiator may be a difunctional compound,including water, so that the resulting polyether is essentially a chainof repeating alkylene oxy groups as in polyethylene ether glycol,polypropylene ether glycol, polybutylene ether glycol and the like; orthe initiator may be any suitable active hydrogen containing compoundwhich may be a monomer or even a compound having a relatively highmolecular weight including other active hydrogen containing compounds asdisclosed herein. It is preferred that the initiator, including as suchamines, alcohols and the like, have from 2 to active sites to which thealkylene oxides may add. Any suitable alkylene oxide may be used suchas, for example, ethylene oxide, propylene oxide, butylene oxide,amylene oxide, tetrahydrofuran, epihalohydrins such as epichlorohydrin,styrene oxide and the like. Any suitable initiator may be usedincluding, for example, water, polyhydric alcohols, preferably having 2to 8 hydroxyl groups, amines, preferably having 2 to 8 replaceablehydrogen atoms bonded to nitrogen atoms and the like. Phosphorous acidsmay also be used, as initiators, but the phosphorous compounds aresomewhat peculiar and require different modes of preparation as moreparticularly set forth below. The resulting polyhydric polyalkyleneethers with the various bases of nitrogen, phosphorous and the like mayhave either primary or secondary hydroxyl groups or mixtures of primaryand secondary hydroxyl groups. It is preferred to use alkylene oxideswhich contain from 2 to 5 carbon atoms and, generally speaking, it isadvantageous to condense from about 5 to about 30 mols of alkylene oxideper functional group of the initiator. There are many suitable processesfor the preparation of polyhydric polyalkylene ethers including US.Patents 1,922,459; 3,009,939 and 3,061,625 or by the process disclosedby Wurtz in 1859 and discussed in the Encyclopedia of ChemicalTechnology, volume 7, pages 257 to 262, published by IntersciencePublishers, Inc. (1951).

Specific examples of initiators are water, ethylene glycol, propyleneglycol, glycerine, trimethylol propane, pentaerythritol, arabitol,sorbitol, maltose, sucrose, ammonia, diethanolamine, triethanolamine,dipropanolamine, tripropanolamine, diethanolpropanolamine,tributanolamine, 2,4-toluene diamine, 4,4-diphenylmethane diamine,p,p,p"-triphenylmethane triamine, ethylene diamine, propylene diamine,propylene triarnine, N,N,N,N-tetrakis- (Z-hydroxypropyl) ethylenediamine, diethylene triamine and the like. The phosphorous containingpolyols are more fully described below.

Any suitable polyhydric polythioether may be used such as, for example,the condensation product of thiodiglycol or the reaction product of apolyhydric alcohol, such as are disclosed herein for the preparation ofthe hydroxyl polyesters, with any other suitable thioetherglycol. Othersuitable polyhydric polythioethers are disclosed in US. Patents2,862,972 and 2,900,368.

Any suitable polyacetal may be used such as, for example, the reactionproduct of formaldehyde or any other suitable aldehyde with a polyhydricalcohol such as those disclosed herein for the preparation of thehydroxyl polyesters.

Any suitable alphatic polyol may be used such as, for example, alkanediols including, for example, ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4- butylene glycol, 1,3-butylene glycol,1,5-pentane diol, 1,4- butane diol, 1,3-pentane diol, 1,6-hexane diol,1,7-heptane diol, 2,2-dimethyl-1,3-propane diol, 1,8-0ctane diol, 1,20-eicosane diol and the like; alkene diols such as, for exam. ple,1-butene-1,4-diol, 1,3-butadiene-1,4-diol, 2-pentene- 1,5-diol,2-hexane-1,6-diol, 2-heptene-1,7-diol and the like; alkyne diols suchas, for example, 2-butyne-1,4-diol, 1,5-hexadyne-1,6-diol and the like;alkane triols such as, for example, 1,3,6-hexanetriol, 1,3,7-heptanetriol, 1,4,8- octane triol, 1,6,12-dodecane triol and the like; alkenetriols such as 1-hexene-1,3,6-triol and the like; alkyne triols such as2-hexyne-l,3,6-triol and the like; alkane tetrols such as, for example,1,2,5,6-hexane tetrol and the like; alkene tetrols such as, for example,3-heptene-1,2,6,7.

tetrol and the like; alkyne tetrols such as, for example,4-octyne-1,2,7,8-tetrol and the like.

Any suitable aliphatic thiol including alkane thiols containing two ormore SH groups may be used such as, for example, 1,2-ethane dithiol,1,2-propane dithiol, 1,3- propane dithiol, 1,6-hexane dithiol,1,3,6-hexane trithiol and the like; alkene thiols such as, for example,Z-butene- 1,4-dithiol and the like; alkyne thiols such as, for example,3-hexyne-1,-6-dithiol and the like.

Any suitable polyamine may be used including, for example, aromaticpolyamines such as p-amino, 1,5-diamino naphthalene, 2,4-diaminotoluene, 1,3,5-benzene triamine, 1,2,3-benzene triamine,1,4,5,8-naphthalene tetramine and the like; aliphatic polyamines suchas, for example, ethylene diamine, 1,3-propylene diamine, 1,4-butylenediamine, 1,3-butylene diamine, diethylene triamine, triethylenetetramine, 1,3,6-hexane triamine, 1,3,5,7-heptane tetramine and thelike; heterocyclic polyamines such as, for example, 2,6-diaminopyridine, 2,4-diamino--aminomethyl pyrimidine,2,5-'diamino-l,3,4-thiadiazole and the like.

Phosphorous containing compounds are often advantageously used becauseof the flame retarding effect which they impart to the resultingplastics. These compounds often contain 1 or 2 phosphorous atoms as anucleus and then have alkylene oxide side chains bonded to thephosphorous nucleus through either phosphate or phosphite type linkages.The phosphate compounds are advantageously prepared by condensing amixture of phosphorous pentoxide and water with an alkylene oxide. It isadvantageous to use mixtures of phosphorous pentoxide and water whichcorrespond to about 80 percent phosphorous pentoxide and about 20percent water, but any amount within the range of about 65 percent to 90percent phosphorous pentoxide and the balance Water may be used, thewhole range being contemplated. The phosphites are advantageouslyprepared in accordance with the method of U8. Patent 3,009,929 wheretriphenyl phosphite, for example, is reacted with a polypropylene etherglycol to prepare a product having a molecular weight of about 500';other suitable processes are also disclosed in the patent. It is alsopossible to use polyethers based on phosphorous which contain nitrogenatoms in addition to the phosphorous atoms. These compounds may berepresented by the general formula wherein R is phenyl or a lower alkylgroup such as, for example, methyl, ethyl, propyl, butyl and the likeand R is an alkylene radical which preferably contains from 1 to 4carbon atoms such as, methylene, ethylene, 1,2- propylene, 1,4-butyleneand the like; a prefer-red compound is dioxyethylene-N,N-bis-(2hydroxyethyl)aminomethyl phosphonate.

Any of the compounds of any of the classes set forth hereinbefore mayalso contain other substitutent's including halogen atoms such as, forexample, chloro, bromo, iodo and the like; nitro groups; alkoxy radicalssuch as, for example, methoxy, ethoxy, propoxy, butoxy and the like;carboalkoxy groups such as, for example, carbomethoxy, carbethoxy andthe like; dialkyl amino groups such as, for example, dimethyl amino,dipropyl amino, methylethyl amino and the like; mercapto, carbonyl,thiocarbonyl, phosphoryl, phosphato and the like groups.

The polymer of tetrahydrofuran, hydrogenated castor oil and the polymerof an olefin such as ethylene and carbon monoxide have been use-d inpreparing polyurethanes heretofore and can be used as the diluent inpracticing the herein-described invention. Suitable polymers of olefinsand carbon monoxide are disclosed in US. Patent 2,839,478.

As used herein, the term resinous component of the reaction mixture is aresin containing the addition prodpct of an aromatic polyamine and analkylene oxide ei- 1G ther alone or in admixture with another organiccompound having reactive hydrogens.

In the preparation of a cellular polyurethane from the uniquecondensates of this invention, an amount of polyisocyanate at leaststoichiomet-rically equivalent to the reactive hydrogen atoms of thecondensate should be used for best results, although an excess of up toabout 2.5 NCO groups per reactive hydrogen atom or even more can beused. Where the condensate is being used in admixture with an organiccompound containing at least two hydrogen atoms which are reactive withNCO groups as a diluent, the amount of polyisocyanate should beincreased accordingly.

Any suitable organic polyisocyanate including aliphatic polyisocyanates,acyclic polyisocyanates, alicyclic polyisocyanates, and heterocyclicpolyisocyanates may be used but best results are obtained with aromaticpolyisocyanates, and they are preferred. Arylene diisocyanates are mostpreferred. For example, one may use the polyisocyanates disclosed inReissue Patent 24,514 including hexamethylene diisocyanate,2,6-toluylene diisocyanate, 2,4-toluylene diisocyanate, a mixture ofabout percent 2,4-toluylene diisocyanate and 20 percent 2,6-tol-uylenediisocyanate, 4,4-diphenyl methane diisocyanate, 4,4'-diphenyl dimethylmethane diisocyanate, 1,5-naphthalene diisocyanate,1-methyl-2,4-diisocyanato S-chlorobenzene, 2,4-diisocyanato-s-triazine,1-methyl-2,4-diisocyanato cyclohexane, p-phenyl diisocyanate,1,4-naphthalene diisocyanate, 4,4,4"-triphenyl methane triisocyanate,the urea diisocyanates including those disclosed in US. Patent2,757,185, and the dimers, trimers and other polymers ofpolyisocyanates, and the like.

It has been discovered that particularly in the production of a rigidpolyurethane foam, a foam having a greater dimensional stability thanthe foams obtained with one of the foregoing substantially chemicallypure polyisocyanates can be obtained from crude 2,4-toluylenediisocyanate and 2,6-toluylene diisocyanate. When toluylene diisocyanateis produced by conventional phosgenation of the corresponding diamine, aproduct containing about percent 2,4- and 2,6-toluylene diisocyanate isobtained from the phosgenator. This product is then usually subject tofractionation to remove any toluylene diamine or other impurities fromthe product. The ordinary refined commercial grade of an 80 percent2,4-toluylene diisocyanate and 20 percent 2,6-toluylene diisocyanatemixture contains at least 99 percent of these isomers. It was found thata 4" x 4" x 1" block of foam prepared from such refined 8 0 percent 2,4-and 20 percent 2,6-toluylene diisocyanate shrink in storage at 158 F.with a relative humidity of 100 percent to 90 percent of its originalvolume in 11 days. A similar block of foam prepared by an identicalprocess and with the same chemicals except that an unrefined 80 percent2,4-toluylene diisocyanate and 20 percent 2,6-toluylene diisocyanate(about 91 percent toluylene diisocyanate) was used did not shrink to 90percent of its original volume until after 13 days exposure to 100percent relative humidity at 158 F. It is therefore preferred to preparea rigid foam according to this invention from an aromaticpolyamine-alkylene oxide adduct and crude 2,4-toluylene diisocyanate and2,6- toluylene diisocyanate mixtures. The most preferred formulationsfor making rigid foam in accordance with this invention contain apropylene oxide-tolylene diamine condensate having a molecular weight ofabout 354 and a mixture of 80 percent 2,4-toluylene diisocyanate and 20percent 2,6-toluylene diisocyanate which is a crude product containingabout 90 percent of the isomers and about 10 percent of lay-products andother impurities obtained from the phosgenation of a mixture of 80percent 2,4-dia1nino toluene and 20 percent 2,6-diamino toluene.

Polyurethane foams can be prepared in accordance with this inventioneasily by a one-shot process in which the resinous component, thepolyisocyanate and the blowing agent are mixed together substantiallysimultaneously. Any

suitable apparatus such as the one disclosed in Reissue Patent 24,514may be used. A one-shot process is preferred over a perpolymer processalthough it is possible to prepare the foam in two steps if the resinouscomponent is reacted first under substantially anhydrous conditions withan organic polyisocyanate to form a prepolymer which is then reactedwith water or mixed with another blowing agent to form the foam in asecond step.

Any suitable material which will emit a gas which can be entrapped inthe polyurethane causing it to expand may be used as the blowing agent.Therefore, the blowing agent can be carbon dioxide produced in thereaction mixture through reaction of water with NCO groups or it can bein the reaction mixture in the form of an added inert gas, such as, forexample, nitrogen, carbon dioxide, air, argon or the like.Trichlorofiuoromethane, or a similar organic compound which is a gas atthe reaction temperature of about 75 C. or less can be used. A mixtureof carbon dioxide produced by reaction of water with NCO groups in thereaction mixture and trichlorofluoromethane, dichlorodifluoromethane,difluorochloroethane, difiuorobromoethane, difiuoro dibromomethane,difluoro dichloroethane, difluro 1,2 dichloroethylene,trifluorotrichloroethane, diethyl ether, methylene chloride, or similarmaterial may be used but it is preferred to use trichlorofluoromethaneor the like, particularly if the foam is to be used as an insulator,such as, for example, in the wall of a refrigerator. Pentane, hexane orsimilar hydrocarbon having a boiling point of 75 C. or less may be used.It has been found that the insulating properties of a foam produced whentrichlorotluoromethane is used as the blowing agent are better than whencarbon dioxide or the like is used alone. If the rigid foam is to beused where maximum strength is important, it is preferred to use carbondioxide either by addition thereof as a gas to the reaction mixture orby forming it in situ in the reaction mixture. Therefore, any suitableinert compound which is a gas at the reaction temperature can be used.Such inert gases and the manipulative steps required for using them areknown and the selection of the blowing agent does not form part of thisinvention.

It is sometimes possible to conduct the reaction to prepare apolyurethane without any catalyst being present, particularly if thepolyamine-alkylene oxide adduct contains a high percentage of -OH and/or contains tertiary nitrogen. However, small amounts of catalyst may beused to advantage in some reaction mixtures. Consequently, the inventioncontemplates either a polyurethane reaction mixture containing nocatalyst or a polyurethane reaction mixture containing any catalyticamount of any suitable catalyst. Some such suitable catalysts may be anysuitable tin compound such as, for example, stannous chloride, stannousoctoate, stannous oleate or any other stannous salt of a carboxylic acidhaving from 1 to 18 carbon atoms; a dialkyl tin salt of a carboxylicacid having from 1 to 18 carbon atoms such as, for example, dibutyl tindi(2-ethyl hexoate), dibutyl tin dilaurate, or the like; dibutyl tindibutoxide, dimethyl tin oxide, dibutyl tin sulfide or any other dialkyltin oxide or dialkyl tin sulfide and the like. Any suitable tertiaryamine may be used either in admixture with the tin compound or alone asa catalyst. Some such suitable tertiary amines are disclosed in ReissuePatent 24,514 and include for example, t riethylene diamine, N-ethylmorpholine, N-methyl morpholine, tetramethyl-l,3-butane diamine,triethyl amine, 1-methyl-4-(dimethyl amino ethyl) piperazine, and thelike. Although any catalytic amount of catalyst is contemplated in thoseembodiments using a catalyst, it is preferred to use from about 0.01 toabout 1 part by weight of the tin compound per 100 parts by weight ofthe resinous component, i.e. the polyamine adduct plus the diluent, orfrom about 0.1 to about 5 parts by weight of a tertiary amine per 100parts of the resinous component of the reaction mixture. Best resultsare obtained when 12 the amount of the tin catalyst is from about 0.05to about 0.3 parts by weight per parts resin, so this amount is mostpreferred. For the tertiary amine, the best results are obtained whenthe amount of tertiary amine is from about 0.2 to about 1 part by weightper 100 parts resin so this amount is most preferred.

It is often advantageous in the production of cellular polyurethaneplastics to include other additives in the reaction mixture such as, forexample, emulsifiers, foam stabilizers, coloring agents, fillers and thelike. It is particularly advantageous to employ an emulsifier such as,for example, sulphonated castor oil and/ or a foam stabilizer such as asilicone oil including, for example, a polydirnethyl siloxane or analkyl silane polyoxyalkylene block copolymer; the latter type ofsilicone oil is disclosed in U.S. Patent 2,834,748. When polyhydricpolyalkylene ethers are used in the preparation of a cellularpolyurethane plastic, it is preferred to employ a silicone oil such asone of those defined in the above patent which comes within the scope ofthe formula O(R2SiO)p(CnHzn0)=R RSi-O(R2SiO) (CnHznO)zR"o(R2sio).(C..I-Ino).R" wherein R, R and R" are alkyl radicals having 1to 4 carbon atoms; p, q and r each have a value of from 4 to 8 and (C HO) is a mixed polyoxyethylene oxypropylene group containing from 15 to19 oxyethylene units and from 11 to 15 oxypropylene units with z equalto from about 26 to about 34. The most preferred compound is one havingthe formula wherein (C H O) is a mixed polyoxyethylene and oxypropyleneblock copolymer containing about 17 oxyethylene units and about 13oxypropylene units. Other suitable stabilizers are disclosed in CanadianPatents 668,537, 668,478 and 670,091, and may therefore have the formulawhere X is an integer and represents the number of trifunctionalsilicone atoms bonded to a single monovalent or polyvalent hydrocarbonradical R; a is an integer having a value of at least 1 and representsthe number of polyoxyalkylene chains in the block copolymer; y is aninteger having a value of at least 3 and denotes the number ofdifunctional siloxane units; It is an integer from 2 to 4 denoting thenumber of carbon atoms in the oxyalkylene group; and z is an integerhaving a value of at least 5 and denotes the length of the oxyalkylenechain. It is to be understood that such compositions of matter aremixtures of block copolymers wherein y and z are of different values andthat any method for determining the chain length of the polysiloxanechains and the polyalkylene chains can only give values which representaverage chain lengths. In the above formula, R represents monovalenthydrocarbon radicals, such as alkyl, aryl or aralkyl radicals and thepolyoxyalkylene chain terminates with a hydrogen atom; R is an alkylradical or a trihydrocarbonsilyl radical having the formula R Si where Ris a monovalent hydrocarbon radical and terminates a siloxane chain, andR represents a monovalent or polyvalent hydrocarbon radical, beingmonovalent when x is 1, divalent when x is 2, trivalent when x is 3,tetravalent when x to 4.

One type of block copolymer, when x in the above formula is one, may bepostulated as follows:

where p+q+r has a minimum value of 3, the other subscrlpts being thesame as in the immediately foregoing .chains are joined to the end ofpolysiloxane chains of the The concentration of the stabilizer can varyover a relatively Wide range but preferably it will lie within the rangeof from about 0.01 to about 3 parts by weight per 100 parts of theresinous components. Most preferably, the amount of stabilizer is aboutfrom 0.5 to 1.0 part by weight per 100 parts of the resinous componentof the polyurethane reaction mixture.

The polyurethane foam product provided by this invention is particularlysuitable for use in filling cavities with insulation and for moldingrigid foam objects due to its improved dimensional stability. Forexample, the product of this invention can be used to advantage formaking a wall panel, for filling the cavity of a refrigerator door, orthe like.

In order to better describe and further clarify the invention, thefollowing are specific embodiments thereof.

Example 1 About 65 parts by weight .of the condensate of 2,4- tolylenediamine and propylene oxide having an average molecular weight of about354 and an hydroxyl number of about 630 and about 35 parts by weight ofthe condensate of hexanetriol and propylene oxide having a molecularweight'of about 700, an hydroxyl number of diamine and about 1.5 partsof the siloxane oxyalkylene block copolymer having the formula wherein(C H O) represents about 17 oxyethylene units and about 13 oxypropyleneunits and the value of z is thus about 30. The diisocyanate and otheringredients .are injected into a stream of the condensate in thisapparatus and mixing of the components is achieved substantiallyinstantaneously.

After the foregoing have been mixed together to form a liquid reactionmixture which is substantially uniform in composition throughout, thereaction mixture is discharged from the mixing apparatus into a cavitywhere chemical reaction occurs and the reaction mixture expands into aporous material which fills the cavity and solidifies into a rigidpolyurethane foam having a density of about 2.3 pounds per cubic foot.The softening point of this product is about 165 C; and the foam when exposed to 100 percent relative humidity at 70 C. for about four weekswill shrink less than percent in volume.

' Example 2 About 70 parts by Weight of the condensate of tolylenediamine and propylene oxide having a molecular weight of about 354,about 30 parts of the condensate of hexanetriol and propylene oxidehaving a molecular weight of about 700 and an hydroxyl number of about240 and a viscosity of about 375 centipoises at 25 0., about 20partstrichlorofluoromethane, about 78 parts of an 80 percent2,4-toluylene diisocyanate and 20 percent 2,6-tolylene diisocyanatemixture, about 0.05 part stannous octoate, about 0.1 parttetramethyl-1,3-butane diamine, and about '1.5 parts of the siloxaneoxyalkylene block copolymer of Example 1 are mixed togethersubstantially simultaneously in an apparatus of the type described inUS. Patent Reissue 24,514. As soon as the components have been mixedinto a reaction mixture of substantially uniform composition, thereaction mixture is discharged from the mixing apparatus into a suitablemold where chemical reaction occurs with the formation of a rigidpolyurethane foam having a density of about 2.2 pounds per cubic footand a softening point of about 170 C. This product fills the mold uponchemical reaction with accompanying expansion and is a solid rigid foamwhich will shrink less than 10 percent in volume when exposed to arelative humidity of percent to percent at 70 C. for four weeks.

Example 3 About 60 parts by weight of the condensate of tolylene diamineand propylene oxide having a molecular weight of about 354 and anhydroxyl number of about 630, about 40 parts of the condensate ofhexanetriol and propylene oxide having a molecular weight of about 700,a viscosity of about 375 centipoises at 25 C., and an hydroxyl number ofabout 240 are mixed together and the resulting mixture is mixed withabout 72 parts by weight of an 80 percent, 2,4-toluylene diisocyanateand 20 percent 2,6- toluylene diisocyanate mixture, about 20 partstrichlorofluoromethane, about 0.1 part stannous oleate, about 0.1 parttetramethyl-lfi-butane diamine and about 1.5 parts of the siloxane.oxyalkylene block copolymer of Example 1 in an apparatus of the typedescribed in US. Patent Reissue 24,514. The resulting mixture isdischarged into a suitable mold where chemical reaction occurs and asolidified rigid foam is obtained having a density of about 2.2 poundsper cubic foot and softening point of about 145.

Example 4 About 60 parts weight of the condensate of propylene oxide andtolylene diamine having a molecular weight of about 354 and an hydroxylnumber'of about 630 and about 40 parts of the condensation product oftrimethylolpropane and propylene oxide having a molecular weight ofabout 420, an hydroxyl number of about 357 and a viscosity of 885centipoises at 25 C. are mixed together. This mixture is then mixed withabout parts of an 80 percent 2,4-toluylene diisocyanate and 20 percent2,6- toluylene diisocyanate mixture, about 0.05 part stannous octoate,about 0.1 part tetramethyl-1,3-butane diamine, about 2.9 parts water andabout 1.5 parts of the siloxane oxyalkylene block copolymer of Example 1in an apparatus of the type described in US. Patent Reissue 24,514.After a uniform mixture is obtained, the liquid is discharged from themixing apparatus into a suitable mold where chemical reaction occurswith the formation of a rigid polyurethane foam having a density ofabout 2.0 pounds per cubic foot and a softening point of about 160 C.

Example 5 About 50 parts by weight of the condensate of propylene oxideand tolylene diamine having a molecular weight of about 354 and anhydroxyl number of about 630 and about 50 parts of the condensationproduct of hexanetriol and propylene oxide having a molecular weight ofabout 700, an hydroxyl number of about 240 and a viscosity of 375centipoises at 25 C. are mixed together. This mixture is then mixed withabout 101 parts of an 80 percent 2,4-toluylene diisocyanate and 20percent 2,6-toluylene diisocyanate mixture, about 0.1 part stannousoleate, about 0.2 part tetramethyl-1,3-butane diamine, about 4 partswater and about 1.5 parts of the siloxane oxyalkylene block copolymer ofExample 1 in an apparatus of the type described in US. Patent Reissue24,514. After a uniform mixture is obtained, the liquid is dischargedfrom the mixing apparatus into a suitable mold where chemical reactionoccurs with the formation of a rigid polyurethane foam having a densityof about 1.2 pounds per cubic foot and a softening point of about C.

1 5 Example 6 About 55 parts by weight of the condensate of propyleneoxide and tolylene diamine having a molecular weight of about 354 and anhydroxyl number of about 630 and about 45 parts of the condensationproduct of hexanetriol and propylene oxide having a molecular weight ofabout 700, an hydroxyl number of about 240 and a viscosity of 375centipoises at 25 C. are mixed together. This mixture is then mixed withabout 71 parts of an 80 percent 2,4- toluylene diisocyanate and 20percent 2,6-toluylene diisocyanate mixture, about 0.1 part stannousoleate, about 0.2 part tetramethyl-1,3-butane diamine, about 20 partstrichlorofluoromethane and about 1.5 parts of the siloxane oxyalkyleneblock copolymer of Example 1 in an apparatus of the type described inUS. Patent Reissue 24,514. After a uniform mixture is obtained, theliquid is discharged from the mixing apparatus into a suitable moldwhere chemical reaction occurs with the formation of a closed cell rigidpolyurethane foam having a density of about 2 pounds per cubic foot anda softening point of about 135 C.

Example 7 About 60 parts by Weight of the condensate propylene oxide andtolylene diamine having a molecular weight of about 354 and an hydroxylnumber of about 630 and about 40 parts of the condensation product oftrimethylolpropane and propylene oxide having a molecular weight ofabout 1535, an hydroxyl number of about 110 and a viscosity of 360centipoises at 25 C. are mixed together. This mixture is then mixed withabout 66 parts of an 80 percent 2,4-toluylene diisocyanate and 20percent 2,6- toluylene diisocyanate mixture, about 0.1 part dibutyl tindilaurate, about 0.2 part 1-methyl-4-dimethyl amino ethyl piperazine,about 20 parts trichlorofiuoromethane and about 0.5 part of the siloxaneoxyalkylene block copolymer of Example 1 in an apparatus of the typedescribed in US. Patent Reissue 24,514. After a uniform mixture isobtained, the liquid is discharged from the mixing apparatus into asuitable mold where chemical reaction occurs with the formation of aclosed cell rigid polyurethane foam having a density of about 2 poundsper cubic foot and a softening point of about 160 C.

Example 8 About 50 parts by weight of the condensate of propylene oxideand tolylene diamine having a molecular weight of about 354 and anhydroxyl number of about 630 an about 50 parts of the condensationproduct of sorbitol and propylene oxide having a molecular weight ofabout 1340, an hydroxyl number of about 286 and a viscosity of 1388centipoises at 25 C. are mixed together. This mixture is then mixed withabout 65 parts of an 80 percent 2,4-toluylene diisocyanate and 20percent 2,6-toluylene diisocyanate mixture, about 0.6 parttettramethyl-1,3- butane diamine, about 20 parts trichlorofluoromethaneand about 1 part of the siloxane oxyalkylene block copolymer of Example1 in an apparatus of the type described in US. Patent Reissue 24,514.After a uniform mixture is obtained, the liquid is discharged from themixing apparatus into a suitable mold where chemical reaction occurswith the formation of a polyurethane foam having a density of about 2.1pounds per cubic foot and a softening point of about 130 C.

Example 9 About 60 parts by weight of the condensate of propylene oxideand tolylene diamine having a molecular weight of about 354 and anhydroxyl number of about 630 and about 40 parts of the condensationproduct of hexanetriol and propylene oxide having a molecular weight ofabout 700, an hydroxyl number of about 240 and a viscosity of 375centipoises at 25 C. are mixed together. This mixture is then mixed withabout 76 parts of a crude 80 percent 2,4-toluylene diisocyanate and 20percent 2,6-toluyl- 16 ene diisocyanate mixture having an assay of 91percent toluylene diisocyanate, about 0.25 part stannous oleate, about20 parts trichlorofluoromethane and about 1 part of the siloxaneoxyalkylene block copolymer of Exam le 1 in an apparatus of the typedescribed in US. Patent Reissue 24,514. After a uniform mixture isobtained, the liquid is discharged from the mixing apparatus into asuitable mold where chemical reaction occurs with the formation of arigid polyurethane foam having a density of about 2.2 pounds per cubicfoot and a softening point of about 150 C.

Example 10 About 65 parts by weight of the condensate of propylene oxideand tolylene diamine having a molecular weight of about 354 and anhydroxyl number of about 630 and about 35 parts of the condensationproduct of trimethylolpropane and propylene oxide having a molecularWeight of about 730, an hydroxyl number of about 230 and a viscosity of412 centipoises at 25 C. are mixed together. This mixture is then mixedwith about 118 parts of a crude 4,4-diphenyl methane diisocyanatemixture containing 44 percent NCO, about 0.05 part stannous oleate,about 0.3 part tetramethyl-1,3-butane diamine, about 25 partstrichlorofluoromethane and about 0.5 part of the siloxane oxyalkyleneblock copolymer of Example 1 in an apparatus of the type described inUS. Patent Reissue 24,514. After a uniform mixture is obtained, theliquid is discharged from the mixing apparatus into a suitable moldwhere chemical reaction occurs with the formation of a rigidpolyurethane foam having a density of about 2.2 pounds per cubic footand a softening point of about 165 C.

Example 11 About 60 parts by weight of the condensate of propylene oxideand tolylene diamine having a molecular weight of about 354 and anhydroxyl number of about 630 and about 40 parts of the condensationproduct of glycerine and propylene oxide having a molecular weight ofabout 650, an hydroxyl number of about 236 and a viscosity of 250centipoises at 25 C. are mixed together. This mixture is then mixed withabout 72 parts of an percent 2,4-toluylene diisocyanate and 20 percent2,6-toluylene diisocyanate mixture, about 0.05 part stannous oleate,about 20 parts trichlorofluoromethane, and about 1.5 parts of thesiloxane oxyalkylene block copolymer of Example 1 in an apparatus of thetype described in US Patent Reissue 24,514. After a uniform mixture isobtained, the liquid is discharged from the mixing apparatus into asuitable mold where chemical reaction occurs with the formation of arigid polyurethane foam having a density of about 2.4 pounds per cubicfoot and a softening point of about C.

Example 12 About 2000 parts of a mixture of 80 percent 2,4- tolylenediamine and about 20 percent 2,6-tolylene diamine are heated to about C.and about 2 grams of sodium metal are added thereto. While rapidlystirring the tolylene diamine, propylene oxide under a pressure of aboutone atmosphere gauge is added until a total of about 3170 parts byweight propylene oxide have been added while cooling the mixture tomaintain a temperature of 160 C. or lower. When reaction hassubstantially subsided, about 5.1 parts benzoyl chloride are added andreacted with the sodium catalyst. The contents of the reaction vesselare then cooled to room temperature. The product thus obtained has anhydroxyl number of 616, an acid number of 0.08 and a viscosity of about2200 centipoises at 73 C. The product contains about 0.14 percent water.

About 100 parts by weight of the product of the foregoing reactionwithout purification are mixed with about 62 parts by weight of amixture of 80 percent 2,4- toluylene diisocyanate and 20 percent2,6-toluylene diisocyanate, about 0.02 part stannous octoate, about 0.2

part 1-methyl-4-dimethyl amino ethyl piperazine, about 20 partstrichlorofluoromethane and about 0.5 part of the siloxane oxyalkyleneblock copolymer used in Example 1 above. After a substantially uniformmixture is obtained, the reaction mixture is placed in a suitablecontainer where reaction proceeds with foaming and expansion of thereaction mixture into a cellular polyurethane plastic which uponsolidification has a density of about 2 pounds per cubic foot.

Example 13 About 100 parts by weight of a tolylene diamine-propyleneoxide condensate having an hydroxyl number of about 400 and a viscosityof about 57,300 at 25 C. are mixed with about 62 parts by weight of an80 percent 2,4-toluylene diisocyanate and 20 percent 2,6-to1uylenediisocyanate mixture, about 0.02 part stannous octoate, about 0.2 part1-methyl-4-dimethyl amino ethyl piperazine, about 20 partstrichlorofluoromethane and about 0.5 part of the siloxane oxyalkyleneblock copolymer of Example 1. The components of the reaction mixturereact upon mixing to form a solidified cellular polyurethane plastichaving a density of about 2 pounds per cubic foot.

Although the invention has been described in considerable detail for thepurpose of illustration, it is to be understood that variations may bemade therein by those skilled in the art without departing from thespirit of the invention and the scope of the claims.

What is claimed is:

1. A method for making polyurethane foam which comprises reacting anorganic polyisocyanate in the presence of a blowing agent with acompound having the formula:

wherein n is an integer of from 2 to 3 and R is a radical having avalence equal to n and obtained by removing n hydrogen atoms from amember selected from the group consisting of and mixtures thereof,wherein R" is selected from the group consisting of a halogen atom, analkyl radical having from 1 to 4 carbon atoms and an alkoxy radicalhaving from 1 to 4 carbon atoms; R is a member selected from the groupconsisting of hydrogen and an alkyl radical having from 1 to 3 carbonatoms and m is an integer of from to 4.

18 2. The process of claim 1 wherein the said adduct has the formulaEN(CH2CH(CH3) OH):] 2

3. The process of claim 1 wherein the said adduct has the formulaEN(CH2CH(CH3) OHM] 4. The process of claim 1 wherein the said adduct hasthe formula 5. The process of claim 1 wherein the said adduct has theformula 6. The process of claim 1 wherein the adduct has the formula F(X) LN (CHzOHOHhl wherein X is a halogen and R is selected from thegroup consisting of hydrogen and an alkyl radical having from 1 to 3carbon atoms.

References Cited DONALD E. CZAJA, Primary Examiner. G. W. RAUCHFUSS,Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,336,245 August 15 1967 J W. Britain It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 2, lines' 5 to 7, 'the'formula should appear as shown belowinstead of as'in' the patent R N(CH ind-OH) column 6 line 60; for"'restinous" read resinous column 8 line 10., .for "2 to" read 2. 110:8.z: .column 9, line 11 for pamino, 1.,5. diamino.' read rn pz-aminoaniline l 5- diaminow-rgrcolumnll,lined, for "perpolymer" readprepolymer acolumn 13,, line 2, for Fof. the" read of the type column17, line' 24, after "foot." insert the followingparagraph:

It is to be :understood that; any... of the other resinous materialsmay. be used. iniithe' foregoing examples The condensateofpolyamine"with.-alkylene. oxide can be a condensate of any ofatheother aromatic polyaminesiandiit is not necessary tov use. a condensatehaving. all four hydrogen atoms on the diaminesubstituted by a.hydroxyalkyl radical derived through condensation with an alkylene.oxide. The hydrogen atom on the nitrogen atom in the. amine ..is anactive hydrogen atom. and will. produce cross-linking. .Any otherpolyisocyanates can. be. substituted. foritheone set forth in theforegoing. examples'.'..Likewise., otherscatalysts or no catalysts.atall .can...be. used. Although-best results are obtainedwhen a.siloxane. oxyalkylene block copolymer is used. asv a. Stabilizer, L. it.is. possible to omit the stabilizer or use any other suitable substituteSigned and sealed this 31st day of December 1968 (SEAL) Attest:

EDWARD M.FLETCHER,JR.. EDWARD. J. BRENNER Attesting Officer Commissionerof Patents

1. A METHOD FOR MAKING POLYURETHANE FOAM WHICH COMPRISES REACTING ANORGANIC POLYISOCYNATE IN THE PRESENCE OF A BLOWING AGENT WITH A COMPOUNDHAVING THE FORMULA: